Polyester composition for use in thermoforming dual-ovenable trays

ABSTRACT

This invention relates to a thermoplastic resin composition which is particularly suitable for use in thermoforming thin-walled articles, such as dual-ovenable trays. Articles which are made utilizing this thermoplastic resin composition have improved low-temperature impact strength. This thermoplastic resin composition is comprised of (a) from about 86 weight percent to about 98 weight percent polyethylene terephthalate having an intrinsic viscosity of at least about 0.7 dl/g; (b) from about 1 weight percent to about 7 weight percent of a polyethylene ionomer; and (c) from about 1 weight percent to about 7 weight percent of a polyolefin with repeat units derived from olefin monomers containing 2 to 6 carbon atoms, wherein the thermoplastic resin composition contains an effective amount of a heat stabilizer. The subject invention also includes thermoforming such thermoplastic resin compositions into thin-walled articles having a crystallinity of from about 10 percent to about 40 percent.

This is a continuation of application Ser. No. 350,292, filed Dec. 6,1994, now abandoned.

FIELD OF THE INVENTION

This invention relates to thermoplastic resin compositions which may beused in a thermoforming process to make dual-ovenable trays. Moreparticularly, this invention relates to a dual-ovenable tray comprising(1) at least 86 weight percent polyethylene terephthalate, (2) not morethan 7 weight percent polyethylene ionomer, and (3) not more than 7weight percent polyolefin.

BACKGROUND OF THE INVENTION

The widespread popularity of microwave ovens for home use has initiatedinterest in food trays which can be used in either microwave ovens orconvection ovens. Such food trays must be able to withstand oventemperatures which approach 200° C. Such trays are of particular valueas containers for frozen prepared foods. It is accordingly necessary forsuch trays to have both good impact strength at freezer temperatures anddimensional stability at oven temperatures. It is, of course, alsoimportant for such trays to be capable of withstanding rapid heatingfrom freezer temperatures of about -30° C. to oven temperatures of about175° C. or even higher.

Containers which are capable of being heated in either convection ovensor microwave ovens are sometimes described as being dual-ovenable.Polyesters are highly suitable for use in making such dual-ovenablecontainers. However, it is important for the polyester to be in thecrystalline state rather than the amorphous state in order to achievesatisfactory high temperature stability. As a general rule,dual-ovenable containers which are comprised of polyester will be heattreated to attain a crystallinity of at least about 15%. Normally,polyesters will undergo crystallization by heat treatment at elevatedtemperatures and the crystallites formed will remain substantiallystable up to near the melting point of the polyester.

Injection molding and thermoforming are widely known methods for formingthermoplastic polyester articles. In injection molding, the polyester isheated above its melting point and injected under sufficient pressure toforce the molten polyester to fill the mold cavity. The molten polyesteris cooled in the mold until it is rigid enough to be removed. However,the injection molding method is generally not satisfactory for theproduction of thin walled articles, such as dual-ovenable trays, due toflow lines and layering which develop during the filling of the mold,which lead to non-uniform properties, surface irregularities, andwarping of the finished article. Very high filling pressures are alsorequired in the injection molding of thin walled articles due to highmelt viscosities.

Thermoforming is another process which is used commercially in theproduction of polyester articles. It is a particularly valuabletechnique for use in producing thin-walled articles, such asdual-ovenable food trays, on a commercial basis. In thermoforming, apreformed polyester sheet is preheated to a temperature sufficient toallow the deformation of the sheet. The sheet is then made to conform tothe contours of a mold by such means as vacuum assist, air pressureassist, or matched mold assist. The thermoformed article produced isnormally heat-treated in the mold in order to attain a crystallinity ofat least about 15%.

The physical properties of polyester polymers can be modified throughaddition of other polymers to form a polyester blend. For example, U.S.Pat. No. 4,572,852 discloses a thermoplastic polyester articleconsisting of (1) polyethylene terephthalate, (2) a polyolefincontaining from 2 to 6 carbon atoms, and (3) an effective amount of aheat stabilizer, which exhibits improved impact resistance and hightemperature dimensional stability. Also, U.S. Pat. No. 5,023,137discloses a thermoplastic polyester article comprising (1) polyethyleneterephthalate, (2) polyethylene ionomer, and optionally (3) an effectiveamount of a heat stabilizer, which exhibits improved low temperatureimpact strength.

Dual-ovenable trays which are comprised of polyester blends are widelyutilized commercially. Polyethylene terephthalate having an intrinsicviscosity of at least about 0.65 dl/g is widely utilized in suchapplications. It is important that the polyethylene terephthalate usedin dual-ovenable trays to have an intrinsic viscosity of at least about0.65 dl/g in order for the article to have acceptable impact strength atlow temperatures, such as those experienced in a freezer.

It would be desirable to improve the low temperature impact strength ofdual-ovenable trays. This is because a certain amount of tray breakageoccurs during transporting of frozen prepared foods which are packedutilizing such trays. Such trays have also been known to break uponbeing dropped after taking them out of home freezers. Thus, it would behighly beneficial to manufacture dual-ovenable trays utilizing amaterial which provides improved low temperature impact strength.

It is an object of this invention to provide an improved thermoplasticresin composition for thermoforming articles, such as dual-ovenabletrays, which exhibit improved low-temperature impact performance.Additional objects and advantages of the subject invention will beevident from the detailed description of the invention below.

SUMMARY OF THE INVENTION

It has been unexpectedly found that a three-component blend of (1)polyethylene terephthalate, (2) a polyethylene ionomer, and (3) apolyolefin containing from 2 to 6 carbon atoms, offers an outstandingcombination of properties, including improved low-temperature impactstrength. Both the polyethylene ionomer and the polyolefin componentspreferably contain, in addition, an effective amount of a heatstabilizer. The compositions find utility in thermoforming heat-set,thin-walled articles such as dual-ovenable trays.

The subject invention accordingly relates to a thermoformed,non-oriented, heat-set, thin-walled article, comprising: (a) from about86 weight percent to about 98 weight percent polyethylene terephthalatehaving an intrinsic viscosity of at least about 0.7 dl/g as measured ina 60:40 phenol:tetrachloroethane mixed solvent system at 30° C.; (b)from about 1 weight percent to about 7 weight percent of a polyethyleneionomer having a melt flow index as measured using ASTM Method D-1238 ofless than about 2 g/10 minutes; (c) from about 1 weight percent to about7 weight percent of a polyolefin with repeat units derived from olefinmonomers containing 2 to 6 carbon atoms, wherein the polyolefin containsan effective amount of a heat stabilizer; and wherein said article has atotal crystallinity of from about 10% to about 40%. Preferably, thepolyethylene ionomer also contains an effective amount of a heatstabilizer.

The subject invention also relates to a process for making heat-set,thin-walled, partially crystalline articles which comprisesthermoforming a substantially amorphous sheet which is comprised of: (a)from about 86 weight percent to about 98 weight percent polyethyleneterephthalate having an intrinsic viscosity of at least about 0.7 dl/gas measured in a 60:40 phenol:tetrachloroethane mixed solvent system at30° C.; (b) from about 1 weight percent to about 7 weight percent of apolyethylene ionomer having a melt flow index as measured using ASTMMethod D-1238 of less than about 2 g/10 minutes; (c) from about 1 weightpercent to about 7 weight percent of a polyolefin with repeat unitsderived from olefin monomers containing 2 to 6 carbon atoms, wherein thepolyolefin contains an effective amount of a heat stabilizer; andwherein the thermoforming is carried out in a heated mold for a timesufficient to achieve a crystallinity in said article of from about 10%to about 40%. Preferably, the polyethylene ionomer also contains aneffective amount of a heat stabilizer.

DETAILED DESCRIPTION OF THE INVENTION

The thermoplastic resin compositions of this invention are comprised ofpolyethylene terephthalate (PET), a polyethylene ionomer, and apolyolefin. Such compositions will normally contain from about 86 weightpercent to about 98 weight percent PET, from about 1 weight percent toabout 7 weight percent polyethylene ionomer, and from about 1 weightpercent to about 7 weight percent polyolefin. It is generally preferredthat the thermoplastic resin compositions of this invention contain fromabout 87 weight percent to about 97 weight percent PET, from about 1weight percent to about 6 weight percent polyethylene ionomer, and fromabout 2 weight percent to about 7 weight percent polyolefin. The mostpreferred compositions of this invention contain from about 90 weightpercent to about 94 weight percent PET, from about 1 weight percent toabout 3 weight percent polyethylene ionomer, and from about 5 weightpercent to about 7 weight percent polyolefin.

PET is comprised of repeat units which are derived from terephthalicacid or a diester thereof and ethylene glycol. The PET utilized in thethermoplastic resin compositions of this invention can be a modifiedPET. Such modified PET can contain small amounts of repeat units whichare derived from diacids other than terephthalic acid and/or glycols inaddition to ethylene glycol. For instance, small amounts of isophthalicacid or a naphthalene dicarboxylic acid can be used in the diacidcomponent utilized in preparing the PET. PET which has been modifiedwith a small amount of a diol containing from 3 to 8 carbon atoms isalso representative of a modified PET which can be used. For instance, asmall amount of 1,4-butane diol can be utilized in the glycol componentused in preparing the modified PET. Normally, no more than about 5weight percent of the repeat units in such modified PET will becomprised of diacids or diols other than a terephthalic acid andethylene glycol. It is, of course, contemplated that diesters of suchdicarboxylic acids and diols can be used. In most cases, such modifiedPET will contain less than about 3% diacids other than terephthalic acidand less than 3% diols other than ethylene glycol. It will normally bepreferred for such modified polyesters to contain only about 1%dicarboxylic acids other than terephthalic acid and/or less than 1%glycols other than ethylene glycol. In any case PET homopolymer is anexcellent choice for utilization in the thermoplastic resin compositionsof this invention.

The PET utilized in the thermoplastic resin compositions of thisinvention will normally have an intrinsic viscosity of at least about0.7 dl/g. In most cases, the PET will have an intrinsic viscosity whichis within the range of about 0.8 dl/g to about 1.4 dl/g. It is generallypreferred for the PET to have an intrinsic viscosity of at least 0.9dl/g with it being more preferred for the PET to have an intrinsicviscosity of about 0.95 dl/g. Intrinsic viscosity is defined as thelimit of the fraction (ln v)/C as C, the concentration of the polymersolution, approaches 0, wherein v is the relative viscosity which ismeasured for several different polymer concentrations in a 60:40 mixedsolvent system of phenol:tetrachloroethane at 30° C.

The polyethylene ionomers which can be utilized in the practice of thisinvention are generally copolymers of ethylene and at least one α,β-ethylenically unsaturated carboxylic acid wherein from about 5 percentto about 90 percent of the carboxylic acid groups are ionized byneutralization with metal ions. The α, β-ethylenically unsaturatedcarboxylic acid can be a monocarboxylic acid, or have more than onecarboxylic group attached to it. The carboxylic acid groups areneutralized with at least one cation from the group consisting ofmetallic cations having a valence of 1 to 3. The polyethylene ionomersused in this invention will have a melt flow index as measured usingASTM Method D-1238 after being dried for 16 hours in a vacuum oven at63° C. of less than about 2 g/10 minutes. It is preferred for thepolyethylene ionomer to have a melt flow index of less than about 1.5g/10 minutes, with it being most preferred for the polyethylene ionomerto have a melt flow index of less than about 1.2 g/10 minutes.

The α, β-ethylenically unsaturated carboxylic acids which can becopolymerized with the ethylene monomer preferably have 3 to 8 carbonatoms. Examples of such acids include acrylic acid, methacrylic acid,ethacrylic acid, itaconic acid, maleic acid, fumaric acid and monoestersof other dicarboxylic acids, such as methyl hydrogen maleate, methylhydrogen fumarate, ethyl hydrogen fumarate, and maleic anhydride, whichis considered to behave like an acid and be an acid in the presentinvention.

The polyethylene ionomer will generally contain from about 2 weightpercent to about 40 weight percent α, β-ethylenically unsaturatedcarboxylic acids and from about 60 weight percent to about 98 weightpercent ethylene. The polyethylene ionomer will more typically containfrom about 3 weight percent to about 20 weight percent α,β-ethylenically unsaturated carboxylic acids and from about 80 weightpercent to about 97 weight percent ethylene. A preferred polyethyleneionomer is a copolymer of ethylene and an α, β-ethylenically unsaturatedmonocarboxylic acid having 3 to 6 carbon atoms. A most preferred α,β-ethylenically unsaturated monocarboxylic acid is acrylic acid.Methacrylic acid is another highly preferred α, β-ethylenicallyunsaturated monocarboxylic acid.

The polyethylene ionomers used in this invention will normally have animpact strength as measured at 23° C. using ASTM Method D-1822S of atleast 1100 KJ/m². It is preferred for the polyethylene ionomer to havean impact strength of at least 1150 KJ/m² with it being most preferredfor the polyethylene ionomer to have an impact strength of at least 1200KJ/m².

U.S. Pat. No. 4,248,990 discloses polyethylene ionomers and a processfor making polyethylene ionomers in greater detail. Polyethyleneionomers which can be used in the practice of this invention arecommercially available from E.I. duPont de Nemours & Company, Inc. andare sold under the tradename SURLYN®. For example, Surlyn® 1605 is apolyethylene ionomer which contains approximately 10% acrylic acid andapproximately 5% sodium acrylate. Surlyn® 9721 is a polyethylene ionomerwhich contains ethylene and methacrylic acid.

The polyolefin which can be utilized in the practice of this inventionis produced from olefin monomers having from 2 to 6 carbon atoms. Theresulting polymer contains repeat units derived from the originalmonomer units. These repeat units differ from the monomers in that theyno longer contain a carbon-carbon double bond. Such polymers include lowdensity polyethylene, high density polyethylene, linear low densitypolyethylene, polypropylene, polyisopropylene, polybutene, polypentene,polymethylpentene. A preferred class of polyolefins is the polyethyleneswith the most preferred type being linear low density polyethylene, asrepresented by products marketed by Dow Chemical under the tradenamesDOWLEX 2045 and 2035.

The thermoplastic resin composition of this invention will preferablycontain one or more heat stabilizers. The inclusion of one or more heatstabilizers has particular utility when the finished article being madefrom the resin composition will be subjected to high service temperatureconditions for long periods of time. The retention of adequate physicalproperties, especially impact strength, is very important inapplications such as food trays for use in dual-ovenable applications.Heat stabilizers as used herein are compounds which demonstrateantioxidant properties, the most important of which is the capacity ofinhibiting oxidation. An effective heat stabilizer in the practice ofthis invention must be capable of protecting the thermoformed articleduring exposure to elevated temperatures. It is generally preferred toincorporate a heat stabilizer into the polyethylene ionomer componentand/or into the polyolefin component of the blend, prior to combiningthe three blend components into the thermoplastic resin composition ofthe invention.

The following compounds are representative examples of useful heatstabilizers which can be incorporated into the thermoplastic resincompositions of this invention: alkylated substituted phenols,bisphenols, thiobisacrylates, aromatic amines, organic phosphites, andpolyphosphites. The particular aromatic amines which demonstratespecific heat stabilizing capabilities include: primary polyamines,diarylamines, bisdiarylamines, alkylated diarylamines,ketone-diarylamine condensation products, aldehyde-amine condensationproducts, and aldehyde imines. Conditions which would be consideredsevere would be those in which the thermoformed article would be exposedto temperatures near 200° C. for periods exceeding about 30 minutes.Preferred heat stabilizers for addition to the polyolefin component ofthe thermoplastic resin composition include the polyphenols whichcontain more than two phenol ring structures. Some representativeexamples of suitable polyphenols includetetrakis(methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)-proprionate)methaneand 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene.Preferred heat stabilizers for the polyethylene ionomer component of thethermoplastic resin composition include organic phosphites andpolyphosphites. A representative phosphite is2,2'-ethylidene-bis(4,6-di-t-butylphenyl)fluorophosphite.

Persons skilled in the art will be able to easily ascertain theeffective amount of heat stabilizer needed, with this amount generallybeing within the range of about 0.005 weight percent to about 0.5 weightpercent, based upon the total weight of the thermoplastic resincomposition. It will normally be preferred for the amount of heatstabilizer utilized to be within the range of 0.01 weight percent to 0.5weight percent, based upon the total weight of the thermoplastic resincomposition. The amount of heat stabilizer used will vary with suchfactors as the degree of protection required, the severity of heatexposure, solubility limitations of the heat stabilizer chosen in thethermoplastic resin composition, and the overall effectiveness of theheat stabilizer.

One or more pigments or colorants can also be added to the thermoplasticresin composition in order to provide it with a desired color. Forinstance, titanium dioxide can be included in the thermoplastic resincomposition in order to provide it with a brilliant white color. One ormore colorants can also be added to the thermoplastic resin compositionin order to provide it with any of a multitude of colors. Such colorantswill normally not act as nucleating agents. Some representative examplesof non-nucleating organic colorants include: phthalocyanine blue,solvent red 135, and disperse yellow 64 (CAS No. 10319-14-9). Many otherdyes of the solvent and disperse groups are also useful for coloring thethermoplastic resin compositions of this invention. The amount ofcolorant or combination of colorants needed to obtain a specific desiredcolor can be easily ascertained by persons skilled in the art.

The thermoplastic resin compositions of this invention can be preparedby simply melt blending the PET with the polyethylene ionomer, thepolyolefin, the heat stabilizer(s), and optionally, a colorant. Suchmelt blending is done at a temperature at which the PET is in the liquidstate. PET homopolymer has a melting point of about 260° C. Since such amelt blending procedure must be carried out above the melting point ofthe PET, it will normally be done at a temperature within the range ofabout 260° C. to 350° C. Normally, it is preferred for the melt blendingprocedure to be carried out at a temperature within the range of about280° C. to 320° C. In such a melt blending procedure, the polyethyleneionomer and polyolefin are simply dispersed throughout the molten PET.Sufficient mixing action will be applied so as to result in theformation of a homogeneous system. In other words, the polyethyleneionomer, polyolefin, and heat stabilizers or colorants added should beuniformly dispersed throughout the PET in order to produce optimalthermoplastic resin compositions. Such a melt blending procedure cancommercially be carried out in extruders which provide sufficientshearing forces so as to result in adequate mixing.

In the preparation of films or sheeting for subsequent use inthermoforming processes, it is extremely important that the polyethyleneionomer and polyolefin be uniformly dispersed throughout the PET to forma homogeneous blend in order to achieve optimum results. A preferredmethod of achieving a homogeneous blend is mechanically blending thePET, polyethylene ionomer, and polyolefin prior to introduction into theextruder. It is also preferred for any heat stabilizers to be blendedinto the polyethylene ionomer and the polyolefin components before theyare mixed with the PET. An alternative method involves the preliminarystep of masterbatching the polyethylene ionomer, polyolefin, and one ormore heat stabilizers, with or without some portion of PET. Such amasterbatch may be melt extruded, pelletized and dried for subsequentaddition to PET.

After the thermoplastic resin compositions of this invention have beenprepared, they can be utilized in making a wide variety of usefularticles of manufacture. The thermoplastic resin compositions of thisinvention have particular value for use as thermoforming compositionsfrom which thin-walled articles such as dual-ovenable trays can be made.The articles of manufacture to which this invention relates arethin-walled thermoformed articles. Thin-walled as used herein meansarticles having wall thicknesses of less than about 1 mm.

Since a partially crystalline finished article is necessary for gooddimensional stability at high temperatures, knowledge of the degree ofcrystallinity or percent of crystallinity is of considerable importance.Density is a convenient method of determining the percent ofcrystallinity since there is a direct relationship between the two for agiven polyester composition. A calibrated gradient column can be usedfor determining density at a particular temperature. The density valuecan then be converted into a percent of crystallinity.

The terms crystallization temperature and crystallization onset are usedinterchangeably to mean the temperature or temperature range in which aregularly repeating morphology, brought about by a combination ofmolecular mobility and secondary bonding forces, is induced in a polymerover a molecular distance of at least several hundred angstroms. Thecrystallization temperature or crystallization onset can be visuallyobserved as the point at which a substantially amorphous, unorientedsheet of PET changes from a translucent, hazy appearance to a whiteappearance.

As used throughout this specification and the appended claims, the termglass transition temperature means that temperature or temperature rangeat which a change in slope appears in the volume versus temperaturecurve for said polymer, and defining a temperature region below whichthe polymer exhibits a glassy characteristic and above which the polymerexhibits a rubbery characteristic. The glass transition temperature(T_(g)) of amorphous polyethylene terephthalate is about 70° C.

Another aspect of this invention relates to a process for producing heatset, thin-walled articles from the thermoplastic resin compositions ofthis invention using conventional thermoforming equipment. The completetechnique consists of the following steps:

1) Forming a substantially amorphous sheet from the homogeneouslyblended thermoplastic resin composition;

2) Preheating the sheet until it softens;

3) Positioning the sheet over the mold;

4) Drawing the preheated sheet onto the heated mold surface;

5) Heatsetting the formed sheet by maintaining sheet contact against theheated mold for a sufficient time period to partially crystallize thesheets; and

6) Stripping the part out of the mold cavity.

The sheeting and film for use in the thermoforming process can be madeby any conventional method, the most common method being by extrusionthrough a flat die. It is important that the sheet or film be quenchedimmediately after extrusion in order to minimize the extent ofcrystallization developed after forming. Depending upon the methodemployed in making the film or sheeting, the intrinsic viscosity of thestarting thermoplastic resin composition may be reduced slightly by thecasting or extrusion process. The thermoformed articles made should haveintrinsic viscosities which are similar to the intrinsic viscosities ofthe film or sheeting from which they are made.

The term substantially amorphous as used herein means a sheet having alevel of crystallinity low enough to enable thermoforming of the sheetto be accomplished with satisfactory mold definition and part formation.In currently available thermoforming processes, the level ofcrystallinity of the preformed sheet should not exceed about 10 percent.

Preheating the substantially amorphous sheet prior to positioning itover the thermoforming mold is necessary in order to achieve the veryshort molding times required for a viable commercial process. The sheetmust be heated above its glass transition temperature and below thepoint at which it sags excessively during positioning over the moldcavity. In the thermoforming process, a sheet temperature which iswithin the range of about 130° C. to about 210° C. and a moldtemperature which is within the range of about 140° C. to about 220° C.will normally be utilized. It is often preferred to use a sheettemperature which is within the range of about 120° C. to about 170° C.and a mold temperature which is within the range of about 165° C. toabout 195° C.

This invention can be practiced by using any of the known thermoformingmethods including vacuum assist, air assist, mechanical plug assist ormatched mold. The mold should be preheated to a temperature sufficientto achieve the degree of crystallinity desired. Selection of the optimummold temperature is dependent upon the type of thermoforming equipment,configuration and wall thickness of the article being molded and otherfactors know to those skilled in the art.

Heatsetting is a term describing the process of thermally inducingpartial crystallization of a polyester article without appreciableorientation being present. In the practice of this invention,heatsetting is achieved by maintaining intimate contact of the film orsheet with the heated mold surface for a sufficient time to achieve alevel of crystallinity which gives adequate physical properties to thefinished part. It has been found that desirable levels of crystallinityshould be about 10 to about 40 percent. For containers to be used inhigh temperature food application, it has been found that crystallinitylevels of at least 15 percent were necessary for adequate dimensionalstability during demolding operations. A preferred range ofcrystallinity is from 15 to 35 percent. This range yields parts withexcellent dimensional stability and impact resistance.

The heat set part can be stripped out of the mold cavity by known meansfor removal. One method, blow back, involves breaking the vacuumestablished between the mold and the formed sheet by the introduction ofcompressed air. In commercial thermoforming operation, the part issubsequently trimmed and the scrap ground and recycled.

The following examples are intended to be illustrative of the invention,rather than limiting its scope.

EXAMPLE 1

A PET resin having an IV of 0.95 dl/g was extruder-blended with 3 weightpercent polyethylene ionomer and 3 weight percent linear low densitypolyethylene (Sample 1A). For comparison, the same PET wasextruder-blended with 3 weight percent polyethylene ionomer (Sample 1B)and with 3 weight percent linear low density polyethylene (Sample 1C).All weight percents identified are based upon total composition weight.The polyolefin in both Sample 1A and Sample 1C contained an effectiveamount of a heat stabilizer. The three samples are identified in Table 1below.

The three samples were blended in a 2.5 inch (6.35 cm) extruder whichwas operated at a temperature within the range of about 260° C. to about300° C., utilizing an extruder speed of about 45 rpm and a dietemperature of about 275 ° C. The extruder utilized a screw whichproduced sufficient shearing force to homogeneously blend the samples.Sheeting with a thickness of 0.03 inches (0.076 cm) was preparedutilizing a chill roll temperature of about 55° C. and a take-up speedof about 5.8 ft/min (176.8 cm/min).

The sheeting was subsequently thermoformed into trays using a standardthermoformer fitted with a mold to make trays that were 5 inches×5inches×1 inch. The thermoforming process was carried out using theoperating parameters identified in Table 1 below for each sample. Traysformed from Sample 1A required both less preheat time in the oven andless time in the mold, a significant reduction in tray molding cycletime. Trays formed from Sample 1B spent considerably longer time in themold due to sticking. Trays formed from Sample 1C formed well and wereeasily released from the mold.

The sheeting and tray samples were analyzed to determine density, whichwas converted to crystallinity, and intrinsic viscosity (IV). For thetrays, density, crystallinity, and IV were determined on both unaged andaged samples, using sections from the bottom portion of the trays. Theaged samples were heated in a convection oven at 400° F. (204° C.) for 1hour. The values for Samples 1A-1C are shown in Table 1 below. Thecrystallinity levels for the trays of all three samples are within therange needed to maintain dimensional stability.

Two different methods were used to measure the low temperature impactstrength of the trays. Falling-projectile-type impact testing was doneon a Custom Scientific Failing Dart Drop Unit using ASTM Method 5379(modified to allow use of the trays described) with a 42 inch drop at-20° F. (-29° C.), and using ASTM Method D1898 on a Dynatup 8250instrument, also at -20° F. (-29° C.). The impact test results forSamples 1A-1C are shown in Table 1 below.

The tray made from Sample 1A exhibited a surprising impact strength at-20° F.: more than two times that of comparative Sample 1C, andsignificantly more than comparative Sample 1B, as measured by the CustomScientific test method. The tray made from Sample 1A also exhibited animpact strength at -20° F. of more than 1.8 times that of ComparativeSample 1C, and significantly more than Comparative Sample 1B, asmeasured by the Dynatup method. This is particularly surprising sincethe impact values for the corresponding sheet were more closely grouped.

                  TABLE 1                                                         ______________________________________                                                Sample 1A Sample 1B  Sample 1C                                                (Illustrative)                                                                          (Comparative)                                                                            (Comparative)                                    ______________________________________                                        Composition                                                                   PET content                                                                             94 wt %     97 wt %    97 wt %                                      Ionomer Content                                                                         3 wt %       3 wt %    --                                           Olefin Content                                                                          3 wt %      --          3 wt %                                      Thermoforming                                                                 Top oven  520° F.                                                                            520° F.                                                                           550° F.                               Bottom oven                                                                             460° F.                                                                            450° F.                                                                           450° F.                               Mold      325° F.                                                                            325° F.                                                                           325° F.                               Oven dwell                                                                              15 sec      16 sec     16 sec                                       Mold dwell                                                                               8 sec      15 sec     10 sec                                       Sheet     295-300° F.                                                                        305° F.                                                                           320° C.                               Density                                                                       Sheet     1.2922      1.3149     1.3116                                       Unaged tray                                                                             1.3226      1.3476     1.3472                                       Aged tray 1.3284      1.3601     1.3567                                       Crystallinity                                                                 Sheet      0%          0%         0%                                          Unaged tray                                                                             27%         29%        32%                                          Aged tray 34%         41%        41%                                          Intrinsic Viscosity                                                           Unaged tray                                                                             0.80        0.79       0.78                                         Aged tray 0.76        0.71       0.79                                         Custom Scientific                                                             Tray      415.6 gm    373.9 gm   204.2 gm                                     Dynatup                                                                       Tray      204.0 lbs   128.3 lbs  112.0 lbs                                    ______________________________________                                    

EXAMPLE 2

Masterbatches of a polyethylene ionomer, and a linear low densitypolyethylene containing an effective amount of a heat stabilizer,combined in ratios of 1:1, 1:3, and 3:1, were prepared using a 1.25 inch(3.18 cm) extruder which provided homogeneous blends. The masterbatchblends were dried after extrusion.

A PET resin having an IV of 1.04 dl/g was extruder blended with thethree masterbatch samples, and with the linear low density polyethylenealone. Sample 2A contained 3 weight percent polyethylene ionomer and 3weight percent linear low density polyethylene, Sample 2B contained 6 wt% polyethylene ionomer and 2 weight percent linear low densitypolyethylene, Sample 2C contained 2 weight percent polyethylene ionomerand 6 weight percent linear low density polyethylene, and Sample 2D(comparative) contained 3 weight percent linear low densitypolyethylene.

Sheeting with a thickness of 0.023 inches (0.058 cm) was prepared asdescribed in Example 1, and the sheeting was used to make standard 5inch×5 inch×1 inch trays, as described in Example 1. In addition, thesheeting was used to make 4-compartment oval frozen dinner trays thatwere 7 inches×9 inches×13/16 inch.

The standard trays were analyzed to determine density and crystallinity,as described in Example 1. The two methods for measuring impactstrength, the Custom Scientific and Dynatup methods described in Example1, were utilized to determine impact strength at -40° F. (-40° C.).Results from these tests are shown in Table 2 below.

An additional "edge drop" impact test was performed on the frozen dinnertrays. The trays were filled with 325 grams of water, frozen, placed ina paperboard box, and dropped from a height of 24 inches. Additionaltests were performed with Samples 2B-2D at heights of 12, 16, 20, 24,28, 32, 36, and 40 inches. Ten duplicates of each sample were used foreach drop height, such that a percent breakage could be determined.Results of these tests are shown in Table 2 below.

The results of the impact tests, particularly the edge drop tests,indicate that the thermoplastic resin compositions of the inventionexhibit surprisingly superior low temperature impact strength.

While certain representative embodiments and details have been shown forthe purpose of illustrating this invention, it will be apparent to thosepersons skilled in this art that various changes and modifications canbe made therein without departing from the scope of this invention.

                  TABLE 2                                                         ______________________________________                                                  Sample                                                                              Sample    Sample   Sample                                               2A    2B        2C       2D                                                   (Illus-                                                                             (Illus-   (Illus-  (Compar-                                             trative)                                                                            trative)  trative) ative)                                     ______________________________________                                        Composition                                                                   PET content 94%     92 wt %   92 wt %                                                                              97 wt %                                  Ionomer Content                                                                           3 wt %  6 wt %    2 wt % --                                       Olefin Content                                                                            3 wt %  2 wt %    6 wt %  3 wt %                                  Density                                                                       Sheet       1.2927  1.2987    1.2985 1.3156                                   Unaged tray 1.3175  1.3201    1.3151 1.3470                                   Aged tray   --      --        --     --                                       Crystallinity                                                                 Sheet        0%      0%        0%     0%                                      Unaged tray 27%     28%       27%    30%                                      Aged tray   --      --        --     --                                       Custom Scientific                                                             Tray        72 gms  124 gms   100 gms                                                                              37 gms                                   Dynatup                                                                       Tray        149 lbs 170 lbs   154 lbs                                                                              115 lbs                                  Edge Drop (breakage)                                                          12 inches           10%        0%    15%                                      16 inches           20%       20%    25%                                      20 inches           25%        5%    65%                                      24 inches   20%     15%       30%    95%                                      24 inches           40%       25%    90%                                      28 inches           60%       15%    90%                                      32 inches           55%       40%    100%                                     36 inches           70%       40%    --                                       40 inches           70%       60%    --                                       ______________________________________                                    

What is claimed is:
 1. A thermoformed, non-oriented, heat-set,thin-walled article, the composition consisting essentially of:(a) fromabout 90 weight percent to about 94 weight percent polyethyleneterephthalate having an intrinsic viscosity of at least 0.7 dl/g, asmeasured in a 60:40 phenol :tetrachloroethane mixed solvent system at30° C.; (b) from about 1 weight percent to about 3 weight percent of apolyethylene ionomer having a melt flow index as measured using ASTMMethod D-1238 of less than 2 grams/10 minute; (c) from about 5 weightpercent to about 7 weight percent of a polyolefin with repeat unitsderived from olefin monomers containing 2 to 6 carbon atoms; and (d) aneffective amount of a heat stabilizer; said article having a totalcrystallinity of from about 10 percent to about 40 percent.
 2. Anarticle as described in claim 1 wherein the polyethylene terephthalatehas an intrinsic viscosity of at least 0.9 dl/g.
 3. An article asdescribed in claim 2 wherein the polyethylene ionomer is a terpolymer ofethylene, acrylic acid, and sodium acrylate.
 4. An article as describedin claim 3 wherein the polyolefin is polyethylene.
 5. An article asdescribed in claim 4 wherein the article is a food container.
 6. Anarticle as described in claim 2 wherein the polyethylene ionomer is apolymer which contains from about 3 weight percent to about 20 weightpercent α, β-ethylenically unsaturated carboxylic acids and from about80 weight percent to about 97 weight percent ethylene, based on totalweight of polyethylene ionomer.
 7. An article as described in claim 6wherein the polyolefin is a linear low density polyethylene.
 8. Anarticle as described in claim 7 wherein the polyethylene ionomer has amelt flow index of less than 1.5 grams/10 minutes.
 9. An article asdescribed in claim 8 which has a crystallinity of from about 15 percentto about 35 percent.
 10. An article as described in claim 9 wherein thearticle is a dual-ovenable tray.
 11. An article as described in claim 1wherein the polyethylene ionomer is a copolymer of ethylene andmethacrylate acid which is from about 5 percent to about 90 percentneutralized with at least one metallic cation having a valence of 1 to3.
 12. A process for making a heat-set, partially crystalline,thin-walled article which comprises thermoforming a substantiallyamorphous sheet which is comprised of:(a) from about 90 weight percentto about 94 weight percent polyethylene terephthalate having anintrinsic viscosity of at least 0.7 dl/g, as measured in a 60:40phenol:tetrachloroethane mixed solvent system at 30° C.; (b) from about1 weight percent to about 3 weight percent of a polyethylene ionomerhaving a valence of 1 to 3 and having a melt flow index as measuredusing ASTM Method D-1238 of less than 2 grams/10 minute; (c) from about5 weight percent to about 7 weight percent of a polyolefin with repeatunits derived from olefin monomers containing 2 to 6 carbon atoms; and(d) an effective amount of a heat stabilizer; said sheet having a totalcrystallinity of from 10 percent to about 40 percent.